CN87105158A - Contain the laminated metal chalcogenide of interlayer chalcogenide and synthetic - Google Patents

Contain the laminated metal chalcogenide of interlayer chalcogenide and synthetic Download PDF

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CN87105158A
CN87105158A CN87105158.3A CN87105158A CN87105158A CN 87105158 A CN87105158 A CN 87105158A CN 87105158 A CN87105158 A CN 87105158A CN 87105158 A CN87105158 A CN 87105158A
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chalcogenide
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stratiform
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interlayer
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CN1016771B (en
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布伦特·艾伦·奥德姆布林克
迈克尔·尤金·兰迪斯
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ExxonMobil Oil Corp
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Abstract

A kind of laminar product, it comprise atomic number be 4,5,12 to 15,20 to 33,38 to 51,56, to 83 with greater than the stratiform chalcogenide of 90 at least a element, with the dagger of the chalcogenide that is selected from least a element in periodic table of elements IB, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIIA, the VIIIA family above-mentioned chalcogenide synusia is separated, having at least a kind of in the chalcogen of this stratiform chalcogenide and described dagger chalcogenide is not oxygen.

Description

The present invention relates to laminated metal chalcogenide that contains the interlayer chalcogenide and preparation method thereof.
Known many stratified materials have three-dimensional structure, and this structure only shows the strongest chemical bonding effect in two dimension.In this class material, stronger chemical bond is formed in the two dimensional surface, and the solid that just forms a three-dimensional is in layer piled up on these planes, but a little less than the interaction between the plane come to want compared with the chemical bond that each single planar junction is lumped together.These more weak keys are normally by the interlayer attraction, and for example Van der Waals force, electrostatic interaction and hydrogen bond cause.Under the situation of electroneutral synusia formation layer structure, at this moment just interact between each layer by Van der Waals force, when sliding relatively between the plane, the energy barrier that occurs in the time of can not running into strong interlayer bonding, thus show lubricity highly.Graphite is exactly an example of this class material.The silicate synusia of many clay materials is to be combined in one by the electrostatic attraction that ion provided between each synusia.In addition, interaction of hydrogen bond can directly betide between the complimentary positions on the adjacent layer, perhaps can be provided by the bridging molecule of interlayer.
Stratified material such as clay can give modification and handle to increase its surface area.Especially can lean on various swellers such as water, ethylene glycol, the absorption of amine and ketone etc. struts synusia, fully increases the distance of interlayer., (for example clay is exposed under the high temperature) when the molecule in occupation of the space is removed, the bedding void of such stratified material just is tending towards subsiding.Therefore, even have the chemical treatment that this class stratified material of the surface area that has increased is not suitable for being used for comprising medium harsh conditions.
The interlayer separation degree can with standard technique for example X-ray diffraction estimate with the establishment of base line spacing, be also referred to as " repeat distance " or " d-spacing ".These numerical value show it for example is that the uppermost margin of a certain synusia is adjacent the distance between the uppermost margin of synusia.If the thickness of layer is known, the interlayer spacing can be determined by the thickness that deducts layer from the baseline spacing.
Now taked the preparation of various method have heat endurance increase the stratified material of interfloor distance.Most of technology rely on and introduce a kind of inorganic " pillared " agent between each synusia of stratified material.For example, United States Patent (USP) 4,216,188 disclose a kind of clay, and it is by very rare colloidal solution of distinct single-layer sheet and contains the metal hydroxides that the crosslinking agent of colloidal metal hydroxide solution is made, and clay is carried out crosslinked making.Yet this method needs the Generation Liquid (less than 1 grams per liter) of a kind of high dilution of clay, so that before the crosslinking agent that adds column-supporting agent and lotus positive electricity each synusia is separated fully.
United States Patent (USP) 4,248,739 have described from the cationic metal complex of the metalloid of the clay of imvite class and for example aluminium and the zirconium prepared stable clay with pillared interlayer that reacts.Get between the gas producing formation that the result generates and open very much and the tool heat endurance.
United States Patent (USP) 4,176 discloses for No. 090 and to have used the clay composition that sandwiches interlayer such as the metal hydroxy complex compound of the polycation of aluminium, zirconium and titanium.Call oneself interfloor distance up to 16
Figure 87105158_IMG1
Yet the calcining sample that is exemplified only is limited to about 9
Figure 87105158_IMG2
These spacings are constant and relevant with the specific size of metal hydroxy complex compound basically.
Silicon-containing material is considered to the desirable material of column-supporting agent with its high heat endurance.United States Patent (USP) 4,367 has been described the clay that sandwiches silica at interlayer No. 163, and it is with siliceous reactant such as ionic silicon complex (for example acetylacetonate of silicon) or neutral substance (SiCl for example 4) dipping clay matrix makes.Before carrying out silicon dipping or in the silicon dipping process, available suitable polar solvent such as carrene, acetone, benzaldehyde, three or tetraalkyl ammonium ion or methyl-sulfoxide make clay swell., this kind method be it seems can only provide the silica of individual layer interlayer, and the result makes has only very little spacing between gas producing formation, promptly measures with X-ray diffraction to be about 2～3
Figure 87105158_IMG3
At first, the invention belongs to a kind of laminar product, it comprises atomic number 4,5,12 to 15,20 to 33,38 to 51,56 to 83 and greater than the stratiform chalcogenide of at least a element in 90, with be selected from the periodic table of elements (Fisher scientific company, catalog number (Cat.No.) 5-702-10,1978) I B, II B, III A, III B, IV A, IV B, V A, V B, VI A, VII A, the chalcogenide dagger of at least a element in the VIII A family, it separates the synusia of stratiform chalcogenide, and having at least a kind of among the chalcogen of stratiform chalcogenide and described dagger chalcogenide is not oxygen.
Preferably described dagger is formed by the poly chalcogenide and described product has at least 20
Figure 87105158_IMG4
The d-spacing.
Concerning application of the present invention, " chalcogenide " this term comprises one group of compound that oxide, sulfide, selenides, tellurides and the polonide of the element of non-VI B family are formed.The chalcogenide of used poly should be thought of as the repetitive that comprises two or more among the present invention, preferably three kinds or the more multiple chalcogenide of unit again.Can believe that the extent of polymerization of interlayer interlayer poly chalcogenide can influence the final interlayer separation degree of laminar product.
Also should be appreciated that, term used herein " stratiform " chalcogenide or oxide are being meant so a kind of material on the letter meaning usually, they are can displacement to be left each other by many, and chalcogenide that the spacing between the adjacent lamina increases or oxide individual layer are formed.Such displacement can be measured with x-ray diffraction technique and/or densitometer method.
Second aspect, the present invention relates to the preparation method of the laminar product that adjacent lamina separated with the dagger of chalcogenide, described dagger chalcogenide is to be selected from periodic table I B, II B, III A, III B, IV A, IV B, V A, V B, VI A, the chalcogenide of at least a element of VII A and VIII A family, it is 4 that this preparation method comprises the steps: to begin with atomic number, 5,12 to 15,20 to 33,38 to 51,56 to 83 and greater than the stratiform chalcogenide of 90 at least a element, layered chalcogenide interlayer contains anion site, depend on physical action to separate each layer of stratiform chalcogenide by introduce a kind of organic cation material to the interlayer anion position, between separated each layer of stratiform chalcogenide, introduce the compound that can be converted into chalcogenide then, and make described compound change into chalcogenide, form the chalcogenide dagger that the adjacent lamina of stratiform chalcogenide is separated.Having at least a kind of among the chalcogen of stratiform chalcogenide and chalcogenide dagger is not oxygen.
Method of the present invention is particularly useful for making the bigger stratiform chalcogenide materials of interfloor distance (d-spacing), for example can obtain interfloor distance greater than 10
Figure 87105158_IMG5
With more preferably greater than 20
Figure 87105158_IMG6
Until up to or even surpass 30
Figure 87105158_IMG7
These materials can bear the harsh conditions running in calcination, for example kept in nitrogen or air about 2 hours under about 450 ℃ of temperature or longer time (for example 4 hours) and the interlayer spacing does not obviously reduce, and promptly decrease is less than 10% approximately.In addition, the stratiform chalcogenide for preparing this class can must carry out the dilution of high power in order to introduce the interlayer sandwich material as sandwich technique is arranged earlier.At last, because the chalcogenide precursor compound is introduced with the electroneutral form, so the quantity that sandwiches the interlayer sandwich material in the stratiform chalcogenide does not depend on the charge density of original stratiform chalcogenide, thus in the final products contained interlayer interlayer chalcogenide size can great changes have taken place.Before generating dagger for the operation that each synusia is strutted in, when the suitability of cationic substance is introduced in decision between each layer, should be taken into account charge density.
The another kind of chalcogen of stratiform chalcogenide and chalcogenide dagger is oxygen preferably.
Method of the present invention utilizes a kind of anion site that contains simultaneously wherein again in conjunction with the parent material of the stratiform chalcogenide of interlayer cation.These interlayer cations can comprise hydrogen ion, hydrogen ion and alkali metal cation.This parent material earlier with " pillared " agent that contains organic cationogen material compound for example the organic ammonium cation handle, causing in the parent material the cationic ion-exchange of interlayer now or to be attached to wherein, thereby each synusia of parent material is strutted.Comprise that at those interlayer cations under the situation of hydrogen or hydrogen ion, the organic cation starting compound can comprise neutral compound, organic amine for example, it is converted into corresponding cation in " pillared " handled.In some cases, wish to remove unnecessary " pillared " agent of non-static combination in the stratiform parent material, with now might be continue the chalcogenide precursor compound of back adding a greater number.Such removal can be by finishing with appropriate solvent flush away column-supporting agent.
Above-mentioned processing has generated the laminated metal chalcogenide that has increased the interlayer separation degree, and the organic cations size that sandwiches is depended in this increase.In one embodiment, carried out a series of organic cation exchange.For example, a kind of organic cation can exchange with the organic cation of another kind of large-size, thereby has increased the interlayer spacing step by step.Layered oxide carries out in water-bearing media with contacting preferably of column-supporting agent, so that between each synusia of the chalcogenide that water is retained in " pillared ".
After ion-exchange, handled with the compound that can transform (preferably by hydrolysis) by the material that organic matter has strutted, change into the chalcogenide dagger that makes the separation of each layer of matrix.Comprise the occasion of hydrolysis in conversion process, can utilize the water that Already in " struts " in the stratiform chalcogenide materials to carry out by organic matter.In the case, can be before poly chalcogenide precursor add, adjust the degree of hydrolysis by the degree that changes the material drying that organic matter has been strutted.
Preferably the organic cation that is deposited between each layer can be removed from the stratiform chalcogenide materials, and unlikelyly disturbed or remove interlayer interlayer chalcogenide or its precursor compound significantly.For example, organic cation such as n-octyl ammonium can be removed by calcination at high temperature, for example calcination under nitrogen or air or chemical oxidation condition, and this step preferably carries out after interlayer chalcogenide precursor has been converted into the chalcogenide dagger.
Product of the present invention, particularly after calcination, show high surface area, for example greater than 200,400 or even 600 meters squared per gram, and have high heat endurance and a hydrothermal stability, make product be very suitable for conversion process as hydrocarbon, for example carrier of the catalyst of cracking and hydrocracking or catalyst.
Be used for stratiform chalcogenide of the present invention and be atomic number and be 4,5,12 to 15,20 to 33,38 to 51,56 to 83 and greater than the stratiform chalcogenide of 90 element.At the dagger chalcogen is not under the situation of oxygen, and the stratiform chalcogenide is oxide preferably.Suitable oxide is aluminium and the oxide of silicon, for example bentonite of picture clay and so on.Though, preferably the stratiform chalcogenide is " non-expansibility ", this term is used for being different from common clay, these unselected clays contain the metal oxide flakes of the octahedral coordination on the silica thin slice that is incorporated into tetrahedral coordination, and this clay when contacting with water substantial (being endless in essence sometimes) expansion can take place.Be a kind of stratiform chalcogenide materials of finger about used " non-expansibility " this term definition of stratiform chalcogenide materials here, when this stratified material of every gram contacts 24 hours with at least 10 gram water under 23 ℃, compare with the material before handling, the increase of d-spacing is not more than 5
Figure 87105158_IMG8
In these materials, comprise H 2Ti 3O 7, Na 2Ti 3O 7And KTiNbO 5And some phyllosilicate, for example magadiite (magadiite), silicon sodium stone (natrosilite), kenyaite (kenyaite), makatite (makatite), alunite water silicon sodium stone (nekoite), water silicon sodium stone (kanemite), okenite (okenite), delhyelite (dehayelite), macdonaldite (macdonaldite) and rhodesite (rhodesite), they are different from expandable clay, do not contain octahedra thin slice, i.e. the lamella of forming with the atom of oxygen atom octahedral coordination.In some cases, found out these phyllosilicates with organic cation starting compound exchange before or in the exchange process, to handle be preferable by contacting with one or more polar organic solvents or water.The organic solvent of used polarity should present the electric dipole moment of at least 3.0 Dubais (D) in gas phase, preferablely be at least 3.5 and preferably be at least about 3.8D.The example of appropriate organic solvent is dimethyl sulfoxide (DMSO) (DMSO) and dimethyl formamide (DMF).Organic compound of selecting for use and electric dipole moment thereof are seen CRC chemistry and physics handbook, 61 editions, and 1980-1981, E-64 is to the E-66 page or leaf.
In a most preferred embodiment, parent material is the stratiform chalcogenide, for example oxide and the layered titanate of titanium, zirconium and hafnium of IV A family metal preferably, three titanates such as the Na that for example especially preferentially select for use 2Ti 3O 7Three titanates are the materials that can supply in a large number on the market, and its structure is by the octahedral anion thin slice of titanium and can be exchanged into interlayer H +And H 3O +The interlayer alkali metal cation of ion is formed.The method of making such material can be at United States Patent (USP) 2,496, finds in 993.As everyone knows, Na 2Ti 3O 7Interfloor distance can use bigger octyl ammonium ion and replace its interlayer sodium ion and increase (seeing Weiss etc., Angew.Chem 72 Jahrg.1960/Nr/2,413-415 page or leaf).Yet it is very responsive to heating to contain organic three titanates, subsides because of adding heat energy removal organic material and causing layer structure.The present invention can be used for introducing a kind of stable poly chalcogenide at adjacent interlayer, preferably comprise a kind of element that is selected from by in silicon, germanium, tin and the plumbous group of forming, poly silica for example, the result forms a kind of heat stable material that keeps its interfloor distance in fact when calcining.
In another most preferred embodiment, the chalcogenide parent material is the phyllosilicate that does not contain octahedra thin slice, perhaps with natural or use with synthesized form, for example magadiite, kenyaite or makatite, they can contain the non-element silicon that can constitute four-coordination in skeleton, for example Al, B, Cr, Fe, Ga, Co, In, Ni and Zr.These phyllosilicates can prepare by cocrystallization under the situation that has needed non-silicon quadrivalent element to exist, or other method is the former non-silicon backbone element that has been present in the phyllosilicate can be replaced it with another kind of four-coordination element.For example, when the kenyaite of boracic in framework was handled with aluminum nitrate, the result was formed on the kenyaite that contains aluminium in its skeleton.
Another embodiment of the present invention belongs to preparation and contains the synthetic magadiite section bar material that is formed support by the poly chalcogenide of non-oxidized substance.Synthetic magadiite is easy to from the aqueous reaction mixture of silica that contains cheap source and caustic alkali metal hydroxide synthetic with hydro-thermal method.The four-coordination element of non-silicon promptly is selected from those elements in the group of being made up of Al, B, Cr, Fe, Ga, Co, In, Ni and Zr, can be added in the reactant mixture, thereby make synthetic magadiite type phyllosilicate.These elements preferably are selected from the group of being made up of Al and Fe, also can add a kind of organic directing agent in reactant mixture.The reactant mixture of synthetic magadiite section bar material can be described below with mol ratio:
SiO 2/ X 2O 3=10 to unlimited, and wherein X can be Al, B, Cr, Co, Fe, Ga and/or Ni
M +OH -/ SiO 2=0 to 0.6(preferably 0.1～0.6) M is any alkali metal
H 2O/SiO 2＝8～500
R/SiO 2＝0～0.4
R can be organically such as benzyltriethylammoinium chloride in the formula, benzyltrimethylammonium chloride, dibenzyl alkyl dimethyl ammonium chloride, N, N '-dimethyl piperazidine, triethylamine, or other quaternary compound or heterocyclic amine
Reactant mixture can keep any fate of 1 to 150 day under 100 to 200 ℃ of temperature, to form product now with following ingredients:
%N=0-3, for example 0 to 0.3
SiO 2/ X 2O 3=10 to unlimited
Wherein X can be in tetrahedral or octahedral position
M 2O/SiO 2=0 to 0.5, for example 0.05～0.1
Zhi Bei layered silicate synthesis material is a low surface area like this.The chalcogenide dagger of introducing non-oxidized substance can increase the surface area of these materials.The situation of another embodiment of the present invention belongs to the synthetic kenyaite section bar material of the poly chalcogenide dagger that contains non-oxidized substance.Kenyaite is a kind of silicic acid of stratiform, at nature with sodium salt Na 2Si 22O 45H 2The O form exists, and can make its sylvite K in the laboratory 2Si 22O 4510H 2O.Synthetic kenyaite is easy to from the reactant mixture of silica that contains cheap source and caustic alkali (preferably KOH) by hydrothermal synthetic.Four-coordination element, particularly B, Al and Zr beyond the silica removal also can be added in the reactant mixture to make synthetic kenyaite phyllosilicate.Al(NO 3) 39H 2O and three Zhong Ding oxygen aluminium are suitable reactants of introducing non-silicon four-coordination element in the kenyaite skeleton.
In the another embodiment of the present invention, prepared the porous molecular sieve materials of high surface from the transition metal non-oxidized substance chalcogenide of stratiform.This material merits attention especially, because they contain its d-track only by partially filled transition metal atoms, the result can produce the bonding of metal to metal in each layer inside, thereby shows catalytic performance extraordinary.
The example of stratiform transition metal chalcogenide is well known in the prior art.Mat.Res.Bull.1974 is seen in their embedding, the 9th phase, 1237 pages, R.Schollhorn and H.Meyer about the structure of these materials with alkali and alkaline-earth metal ions; " Intercalation Chemistry " Academic publishing house, New York, the argumentation of 1982,229 pages of A.J.Jacobson.The organic ammonium ion also can occupy the interlayer region of these materials, and R.Schollhorn is seen in relevant argumentation, H.Zagefka, T.Butz, A.Lerf; Mat.Res, Bull.1979,14,369; R.Schollhorn, E.Sick, A.Lerf, Mat.Res.Bull., 1975,10,1005; A.Weiss, R.Ruthardt, Z.Natur.Forsch., 1973,286,249 and R.Schollhorn, E.Sick. and A.Weiss, Z.Natur.Forsch., 1973,286,168.
The chemical formula of suitable stratiform transition metal chalcogenide is MX 2, X is the element that is selected from the group of being made up of S, Se and Te in the formula, M is a kind of transition metal that is selected from periodic table of elements IV A, IV B, V A, VI A, VII A and each family of VIII A.M preferably is selected from Ti, Zr, Hf(IV A family), Sn, Pb(IV B family), V, Nb, Ta(V A family) and, Mo, W(VI A family), Tc, Re(VII A family) and Pt(VIII family) in the group formed.M can be octahedral coordination and/or the coordination of triangular prism shape with the X atom.X is S preferably, so TiS 2Be particularly suitable for the present invention and make stratified material.
These laminated metal two chalcogenide materials are normally electroneutral.Though they can be reduced, for example be reduced, as at MS by contacting with a kind of aqueous solution that plays the alkali metal salt of reducing agent effect 2Under the material situation by Na 2S 2O 4Reduction.Other reducing agent can comprise the alkaline metal salt of borohydrides or sulfide.The reduction of stratified material causes between each layer the existence because of alkali metal ion to reach on every layer of balance having formed negative electrical charge.Continue after handle with column-supporting agent, if particularly column-supporting agent is a cationic, then this pillared processing can be handled and be significantly strengthened owing to reduction.Yet handle even without such reduction, use MX 2Material can absorb the bloated agent of neutral support in a large number.Certainly, the support that the is incorporated into stratified material for example quantity of n-alkylamine of agent that expands can be depending on the person's character of layer interior metallic atom, i.e. the electronic energy level structure of stratified material.After also can influencing, this will be absorbed in the chalcogenide precursor of the poly between each layer, for example as the quantity of the poly oxide precursor of tetraethyl orthosilicate ester and so on.
Form the laminated metal two chalcogenide MX of dagger with method of the present invention 2, particularly wherein X is those materials of sulphur, is considered to be suitable for the usefulness of PETROLEUM PROCESSING, in particular for remove the process of heteroatom from resid feed.
Be applicable to the layered oxide that another kind of layered oxide material of the present invention is a perovskite.The layered oxide of perovskite is well-known in prior art and the report of many this respects arranged, M.Dion for example, M.Ganne, M.Tournoux, Mat.Res. Bull., 1981,16,1429; F.Galasso, " performance of perovskite-type compounds and preparation ", Pergamon publishing house, 1969; Jacobson etc., Inorg.Chem., 1985,24,3727.These materials and the analog that has expanded with organic matter support thereof, for example at U.S. Patent number 4,593, the discloseder material that has expanded with the octyl amine support in 013.Can in this class material, sandwich the dagger of non-oxidized substance chalcogenide with method of the present invention.
The layered oxide of used here perovskite can be used molecular formula M m(A N-1B nO 3n+1) expression, though the anoxic mutation compound of this formula also is well known, and also can adopt.In this molecular formula, M is the interlayer cation of charge balance effect; (A N-1B nO 3n+1) represent the synusia of perovskite, wherein A is more than one metallic atoms that can occupy 12 coordination positions, and B is a kind of metallic atom that can occupy 6 coordination positions, and m preferably is less than or equal to 1 greater than 0; With n more than or equal to 2, preferably 3 to 7.Every layer of BO that includes common summit 6Octahedra by cube arranging, A occupies 12 coordination positions of each cubical center.For purposes of the invention, " cube arrange " this term can comprise under any universal significance cube or accurate cube arrange.
Every layer thickness is with BO 6Octahedral number meter is represented with n.In other words, each layer thickness can be at 3-7 BO 6Change between the octahedron, decide on the stratified material of various perovskites.Its each layer of stratified material of the perovskite of handling with method of the present invention preferably has low charge density, with now before the chalcogenide precursor with poly embeds, possesses and sandwiches the necessary ion-exchange character of more common column-supporting agent.Though each chemical formula unit of the stratified material of some perovskite has two or more charge density, with the charge density of the stratified material of the handled perovskite of the present invention preferably 1 or lower.Though greater than 1 occasion, the column-supporting agent with essential shape and electric charge is to exchange with the interlayer cation in the material at m.
M in the above-mentioned perovskite molecular formula can be the cation of monovalence, divalence or trivalent, preferably is selected from by Li, Na, K, Rb, Cs, NH 4Monovalent cation in the group of forming with H, and A be selected from the group that I A, II A and each family's lanthanide series of III B form one or more one, two or Tricationic, B is the transition metal that is selected from one or more kinds of Re and IV B, V B and VI B family.In a preferred embodiment, A N-1Can be Ca 2Na N-3With B be Nb; In other words, calcium titanium ore bed Ca 2Na N-3Nb nO 3n+1Chemical formulation.In the case, preferably M is that k and n are 3, for example KCa 2Nb 3O 10
According to the present invention, contain in the process of perovskite layered oxide of dagger in preparation, found out that the precursor that utilizes cationic substance or anionic species is being higher than environment temperature, it is beneficial carrying out bloated processing of step support under for example 70 to 110 ℃ (for example about 100 ℃).Similarly, the chalcogenide precursor of the non-oxidized substance poly of interlayer preferably also is being higher than for example 70 to 100 ℃ of environment temperatures, and (for example about 80 to 90 ℃) are introduced in the layered oxide down.
Layered oxide preferably is every layer and has general formula (M x yZ 2-(x+y)O 4) Q-Layered metal oxide, wherein M is the metal of at least a n valency, n is the integer between 0 and 7, represents the room, Z is a tetravalent metal, preferably titanium and wherein
Q=4y-x(n-4) and preferably 0.6～0.9
0＜x+y＜2
Sandwich between each synusia of oxide will be that the electric charge of electric charge balanced action is the cation A of m.Wherein m is the integer between 1 and 3, preferably 1.A preferably is selected from a kind of big alkali metal cation in the group of being made up of Cs, Rb and K, and M is at least a divalence or the trivalent metal cation that is selected from the group of being made up of Mg, Sc, Mn, Fe, Cr, Ni, Cu, Zn, In, Ga and Al.For example M can be In and Ga.On structure, these metal oxides are by multilayer (M x yZ 1-x-yO 6) octahedra constitute, they are to link to each other with trans limit altogether on the one dimension direction, and the limit is continuous altogether for cis on another dimension direction, are formed on the third dimension direction dioctahedron layer by cation A separated.The metal of this formula can be by the starting compound to (1) metal (M) oxide for titanate material, and the mixture that (2) alkali carbonate or nitrate and (3) titanium dioxide are formed carries out high-temperature fusion and prepares; Perhaps the mixture of alkali-metal metal acid-salt and titanium dioxide being carried out fusion prepares.After reactant fully ground to form uniform mixture, such fusion can be carried out under the temperature in 600 to 1100 ℃ temperature range in the air in the porcelain crucible.Before carrying out the bloated processing of organic matter support and sandwiching the chalcogenide operation of poly, products therefrom is ground to 20 to 250 orders, preferably about 100 orders earlier.Use aforementioned " column-supporting agent " for example moisture halogenated alkyl ammonium (as chlorination octyl group ammonium) to handle this levigate metal then for titanate stratiform material.Found out for fear of metal and to be necessary the hydrogen ion concentration that keeps low for the decomposition of titanate and avoid the preferential adsorption of hydrogen ion on column-supporting agent.In with the column-supporting agent processing procedure, the PH scope that adopts is 6～10 usually, best 7～8.5.After this handles, found that before handling with the column-supporting agent of The suitable solvent flush away surplus, water flushing subsequently is favourable with the chalcogenide precursor.Such flushing makes metal that the chalcogenide precursor sandwiches stratiform morely in the titanate, and water treatment then can make the hydrolytic process that helps this kind precursor compound between the water penetrating layer.
Can be referring to following document about the laminated metal for more detailed narration of titanate material and preparation method thereof:
A.F.Reid，W.G.Mumme，A.D.Wadley;Acta.Cryst.，1968，B24，1228;D.Groult，C.Mercy，B.Raveau，J.Solid.State，Chem.，1980，32，289;W.A.England;J.E.Burkett;J.B.Goodenough;P.J.Wiseman;J.Solid.State.Chem.，1983，49，300。
Adopt above-mentioned layered metal oxide as laminated metal of the present invention chalcogenide, multiple different metal atom is mixed in the processed stratiform chalcogenide materials, it can make potential catalytic activity position join among the stable chalcogenide synusia itself.In addition, can add the metallic atom of varying number so that the activity of the required the best of special process to be provided.Moreover metal presents the infinitely great trans layer structure on limit altogether for titanate, rather than resembles for example Na 2Ti 3O 7Such shape 3-body structure (Sheared 3-block structure) that cuts, when this just can reduce or eliminate the sandwich material calcination because thermal decomposition or hydrothermal decomposition and may cause the fracture of synusia.This metalloid may have for titanate material even the heat endurance higher than silicotitanate molecular sieve.In addition, because the wherein different states of oxidation of metallic atom and different stoicheiometries thereof, the different charge densities that may exist on the metal oxide layer in these layered metal oxide materials, thus the quantity that enables to exchange the organic cation material that goes in the material into also can change.And this is also changed the ultimate density of the chalcogenide dagger between each layer of end product.
According to method of the present invention, before the chalcogenide starting compound that adds poly, earlier with forming cationic organic compound for example You Ji Phosphonium or organic ammonium ion processing stratiform chalcogenide materials.Organic cation sandwiching between adjacent layer can physically be separated each layer, and its mode is to make the stratiform chalcogenide be easy to accept to add electroneutral, the hydrolyzable chalcogenide precursor compound of its interlayer.Especially find out that the alkyl cation is useful especially to the present invention.Like this, C 3Bigger alkylammonium, for example the n-octyl ammonium cation is convenient to be combined in the interlayer space of stratiform chalcogenide, plays the effect that each synusia is strutted, and the chalcogenide precursor is sandwiched.The limit that interfloor distance separates can be controlled by the size of used organic ammonium ion, so can reach 2-5 with the n-pro-pyl ammonium cation
Figure 87105158_IMG9
The interlayer spacing, and desire to make interlayer to strut 10 to 20 The cation that then needs n-octyl ammonium cation or equivalent length.Certainly, whether organic cations size and shape can influence it and can sandwich fully in the stratiform chalcogenide structure and go.For example, it is undesirable that bulky cation is used for the present invention as tetrapropyl ammonium, and preferably adopts positive alkyl ammonium cation, for example those cations and the R that derives from positive alkylamine 3R ' N +Cation, R is methyl or ethyl in the formula, R ' is a positive alkyl group that has 5 carbon atoms at least.The organic ammonium cation that separates the chalcogenide synusia also can be by a kind of neutral amine material and stratiform chalcogenide parent material interlayer hydrogen or hydrogen ion react in position and form.On the other hand, interlayer anion at stratiform chalcogenide parent material is under the situation of alkali metal cation, can be at first by making a kind of amine and a kind of aqueous acid, for example hydrochloric acid chemical combination uses the organic ammonium deionized water solution that is generated to handle the stratiform chalcogenide to form organic ammonium cation then.In both cases, processing procedure all is preferably in the aqueous medium carries out, so that can obtain electroneutral, the hydrolyzable chalcogenide precursor in the product that water come hydrolysis to be added in subsequently " pillared ".
The interlayer chalcogenide dagger that between each synusia of chalcogenide parent material, forms, can comprise a kind of chalcogenide, preferably oxide or sulfide, its metallic element is zirconium or titanium, or preferably be selected from periodic table (Fischer scientific company, catalog number (Cat.No.) 5-702-10,1978) a kind of non-carbon of IV B family, i.e. silicon, germanium, tin and lead.Other such element can comprise the element of V A family, for example V, Nb and Ta; II A family element, for example Mg; Or III B family element, for example B.It would be desirable that when the stratiform parent material was the chalcogenide of non-oxidized substance, dagger comprised the silica of poly; With when the stratiform parent material is oxide, comprise titanium disulfide.In addition, the chalcogenide dagger can comprise a kind of element that the acid position with catalytic activity can be provided, preferably aluminium in dagger.
The chalcogenide dagger forms from precursor material, preferably with this precursor material as cationic or be more preferably compound electroneutral, hydrolyzable this required element, for example introduce between each layer that struts to organic matter with the form of the compound of IV B family element.It is the organo-metallic compound of liquid that precursor material is preferably under the ambient environmental conditions.Especially utilize the hydrolyzable compound of required dagger element, for example alkoxide is as precursor.The poly silicon oxide precursor materials that is fit to comprises the tetraalkyl esters of silicon acis, for example the tetraethyl orthosilicate ester selected for use of the positive esters of silicon acis of tetrapropyl, the positive esters of silicon acis of tetramethyl and override.In dagger, also need to comprise the occasion of alundum (Al, contact front and back or while with silicon compound, the aluminium compound of hydrolysis is contacted with organic pillared material at the stratiform chalcogenide.Preferably used hydrolyzable aluminium compound is an aluminum alkoxide, for example aluminum isopropoxide.If dagger must comprise titanium dioxide, can be with hydrolyzable compound, for example titanium isopropoxide as the alkoxytitanium.
In addition, the chalcogenide precursor can contain zeolite precursor, and it can place under the conversion condition, and the zeolitic material that consequently forms interlayer is as the part of chalcogenide dagger at least.In the case, organic-pillared dose of starting compound with the interlayer cation exchange can serve as the synthetic directing agent of zeolite.The interlayer organic cation starting compound that is fit to can comprise monoalkyl primary amine or monoalkyl uncle ammonium ion, for example n-octylamine or n-octyl ammonium ion.U.S. Patent number 4,151,189 disclose the reactant and the condition of the zeolite component that is suitable for forming this embodiment.This patent disclosure be suitable for aluminium, silicon and the alkali metal oxide of the synthetic usefulness of zeolite, and for example organic nitrogen cation that is suitable for using as the synthetic directing agent of zeolite is (as C 4-C 10The n-alkylamine).The suitable source of alundum (Al comprises sodium aluminate, aluminum sulfate and alum soil, and alkali-metal suitable source comprises for example NaOH of alkali-metal hydroxide.Proper reaction conditions comprises that the stratified material that will contain zeolite precursor is heated to from 99 ℃ to 260 ℃ temperature, and from 6 hours to 60 days, preferably 149 ℃ to 232 ℃ kept 12 hours to 8 days during the maintenance.
Through hydrolysis formation chalcogenide dagger with through after organic-pillared dose of the calcination removal, final dagger product can contain residual tradable cation.In stratified material, so residual cation can carry out ion-exchange with other cationic material by known method, to provide or to change the catalytic activity of dagger product.Suitable replacement cation comprises caesium, cerium, cobalt, nickel, copper, zinc, manganese, platinum, lanthanum, aluminium, ammonium, hydrogen ion and composition thereof.
When as catalyst, then wish to sandwich in the dagger product of the present invention other and can tolerate temperature and the material of other condition, the i.e. matrix of using in the organic conversion process.These materials comprise active and inactive material and synthetic or naturally occurring zeolite, equally also comprise the inorganic material of clay, silica and/or metal oxide and so on.The latter can be naturally occurring, also can be to exist with gelatinous precipitate or gel form, and they comprise the mixture of silica and metal oxide.Dagger product and the matrix bond usefulness of getting up is exactly the combination of their activity, can improve conversion ratio and/or selection of catalysts in some organic transformation process.Non-active material can play the effect of diluent, the amount that control transforms in given process, thereby can make product economically, and needn't control reaction speed with other method.These materials can be added in naturally occurring clay such as bentonite and the kaolin, to improve the crushing strength of catalyst under factory's operating condition.In catalyst, above-mentioned material is that clay, oxide etc. play adhesive.Because in industrial use, wish to prevent that catalyst is broken into the material of powder sample, good crushing strength arranged so wish the catalyst of making.At present adopt this class clay adhesive generally just to use for the crushing strength of improving catalyst.
Can imvite and kaolin families be arranged with the compound natural clay of dagger product, this comprises sub-Ben and is commonly referred to the kaolin of rice soil (McNamee), Georgia soil (Georgia) and Florida's soil (Florida) in the Di Kexi soil (Dixie), Mike, perhaps other various essential mineral compositions clay that is galapectite, kaolinite, dickite, nacrite or anauxite.Feed states when this class clay comes out with original exploitation just can be used, and perhaps uses through after calcination, acid treatment or the chemical modification earlier.Comprise inorganic oxide again with the matrix material of the compound usefulness of dagger product, especially aluminium oxide or silica.
Except that above material, dagger product of the present invention can with the matrix material of porous for example aluminum phosphate, silica-alumina, silica-magnesia, silica-zirconia, siliceous thorium oxide, silica-beryllium oxide, silica-titanium oxide, also have ternary complex such as silica-alumina-thorium oxide, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia to carry out compound.The relative scale of dagger product particulate and inorganic oxide gel matrix can be done change in a big way, the dagger product content can be from 1 to 90%(weight), say more generally that especially under the situation of the compound of making pearl or extrudate shape dagger product can account for the 2-80%(weight of compound).
With reference to following example the present invention is narrated.
Example 1
(a) silicas of 400 gram trade mark Cabosil are mixed in 54.4 gram 98%NaOH and 1.4 kg water make gel.Gel was kept 23 days down at 100 ℃ in 2 liters of polypropylene vial, make it crystallization and make synthetic magadiite, filter then, use the hot water injection, the oven dry of under 250, spending the night.Dry products has following composition (weight %):
SiO 283.3
Na 2O 6.9
Al 2O 30.01
The products of getting 100 gram oven dry are added in 600 ml distilled waters, with 0.1N HCl titration to PH be 2, be maintenance 24 hours under 2 the condition at PH.After filtering, air-dry on filter with 8 liters of distilled water flushings, products obtained therefrom contains the Na of 95ppm.
The product (80 gram) that generates is used in the solution-treated 24 hours that contains 80 gram octyl amines among the 160 gram DMSO, filters, air-dry, keep the processing of doing subsequently then.
(b) the dagger product samples of 20 grams above-mentioned (a) are reacted earlier with hydrogen sulfide, with now with H 2Between the S introducing layer, react with 100 gram tetra isopropyl titanium oxide samples then.The reaction of tetra isopropyl titanium oxide was at room temperature carried out 3 days in the polypropylene vial of a sealing, after this filtered formed thin pulp, and is air-dry and in 538 ℃ (1000) calcination 2 hours in air.This product is with the magadiite of titanium disulfide as dagger.
Example 2
With 10.0 gram laminated metal two chalcogenide TiS 2By with 1 mole of Na 2S 2O 4Aqueous solution contact is reduced.With reduzate and 11.5 gram n-octylamine, 8.4 gram 37.1%HCl and 100 gram H 2O places the heat-resistant glass tube of emptying sealing.This pipe is heated to 100 ℃ kept 4 days, after this with the filtration of the material inside the pipe and air-dry.This product stirred one day in the water of anaerobic, flowed down at nitrogen then and filtered and drying.The solid that will obtain so then restrains solid with tetraethyl orthosilicate ester TEOS(5 gram TEOS/) handled 72 hours.In nitrogen, filter and drying after, this solid in nitrogen in 500 ℃ of following calcinations 4 hours.The result generates the TiS of silica as dagger 2Compared with TiS 2Parent material shows bigger to the suction-operated of n-hexane and water and bigger surface area.

Claims (11)

1, a kind of laminar product, this product comprises that atomic number is 4,5,12 to 15,20 to 33,38 to 51,56 to 83 and greater than the stratiform chalcogenide of 90 at least a element, dagger with the chalcogenide of at least a element that is selected from periodic table of elements I B, II B, III A, III B, IV A, IV B, V A, V B, VI A, VII A, VIII A family, this dagger separates this chalcogenide synusia, and at least a element is not an oxygen in the chalcogen of the chalcogenide of stratiform chalcogenide and described dagger.
2, the product of claim 1, wherein said stratiform chalcogenide right and wrong expansile (as herein defined).
3, the product of claim 1, wherein said chalcogenide are the chalcogenides that a kind of layered oxide and described dagger comprise a kind of non-oxidized substance at least.
4, the product of claim 3, wherein said layered oxide are a kind of phyllosilicate, layered titanate, layered oxide, and wherein each layer has the structure of perovskite, or a kind of layered metal oxide, and wherein every layer has following general formula
〔Mx□yZ 2-（x+y）O 4〕 q-
M is the metal of at least a n valency in the formula, and n is from 0 to 7 integer here, and represents the room, and Z is a kind of tetravalent metal, wherein
q＝4y-x（n-4）
With 0＜x+y＜2.
5, the product of claim 3, wherein said dagger comprises a kind of sulfide.
6, the product of claim 1, wherein said stratiform chalcogenide meets chemical formula MX 2, M is that transition metal and X are S, Se or Te here.
7, the product of claim 6, dagger is wherein formed by oxide.
8, the product of claim 7, dagger wherein comprises the silica of poly.
9, the preparation method of the laminar product of claim 1, may further comprise the steps: beginning with atomic number is 4,5,12 to 15,20 to 33,38 to 51,56 to 83 and greater than the stratiform chalcogenide of 90 at least a element, layered chalcogenide interlayer contains anion site, by introduce a kind of organic cation material to the interlayer anion position, make each layer of stratiform chalcogenide depend on physical action to separate, be separated between each layer to introduce a kind of compound that can change into chalcogenide to the stratiform chalcogenide, described compound is converted into the chalcogenide dagger, the adjacent lamina of stratiform chalcogenide is separated, and having at least a kind of in the chalcogen of stratiform chalcogenide and chalcogenide dagger is not oxygen.
10, the method for claim 9, wherein said organic cation material is an alkyl ammonium cation.
11, a kind of carbon monoxide-olefin polymeric, it comprises laminar product as claimed in claim 1 and a kind of matrix material.
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